Light-sensitive photographic elements containing developing agent precursors



United States Patent 3,287,129 LIGHT SENSITIVE PHOTOGRAPHIC ELEMENTS ggllfsTAlNlNG DEVELOPING AGENT PRECUR- William W. Rees, Elliott Frauenglass, and John W. Gates,

Jr., Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N0 Drawing. Filed Jan. 16, 1963, Ser. No. 251,750 20 Claims. (CI. 96-35) This invention relates to light-sensitive photographic silver halide emulsions and more particularly to photographic silver halide emulsions which contain a photographically compatible precursor of a silver halide developing agent.

It is known to incorporate certain silver halide developing agents in photographic silver halide emulsion layers. Such'emulsions are developed after light exposure, by treating them in alkaline solutions which may or may not contain a developing agent. Following development, the developed silver image is fixed by treating the developed silver halide layer in a conventional sodium thiosulfate fixing bath. The developed and fixed photographic emulsion layer is then washed and dried.

Light-sensitive silver halide emulsion layers containing a silver halide developing agent tend to have less stability on storage than is desired.

It is also well known in the photographic art to employ developing agents, the oxidation products of which react with gelatin to raise its melting point, harden or tan, it so as to modify its physical properties. The layer can then be subjected to warm water to remove the untanned gelatin in the undeveloped or background areas, leaving a gelatin relief containing a silver image. This gelatin relief, by virtue of the density provided by the silver image, comprises a usable photograph. Alternatively the difference in absorption between the gelatin relief areas and the background can be used for imbibition of dye solutions for transfer to mordanted receiving sheets; the relief can be used in photochemical processes, such as topography or gravure; the difference in ink-water receptivity of the gelatin relief and the hydrophobic support can be employed in lithographic printing. The relief can be transferred to other support, such as silk screen for stencil printing and the like. Alternatively, the difference in the ink receptivity of the hardened and unhardened areas can be employed directly without wash ofi as in the lithographic printing process of US. patent application Serial No. 861,125, filed December 21, 1959, now US. Patent No. 3,146,104.

A process of this kind is also used in colloid transfer systems such as that of US. Patent 2,596,756, issued May 13, 1952. I 1

In the usual process of photographic development, the exposed photographic element comprising a support having at least one gelatino-silver-halide emulsion layer thereon, is immersed in a developing bath containing a silver halide photographic developing agent. The developing bath is normally maintained as a separate processing bath and with continuous use, the bath usually becomes less eflicient so that special techniques and replenishments are normally required to maintain optimum processing efficiency. The developing baths of the prior art normally contain a developing agent, a preservative, such as sodium sulfite, and alkali to activate the developing agent, and may also contain other materials, such as sodium bromide (restrainer), antifoggants, etc.

In many processes of the kind mentioned in the foregoing, it has been proposed to incorporate the tanning silver halide developing agent directly in the sensitive emulsion. Although this is convenient, it is frequently disadvantageous because the tanning developing agent in exposure to a silver image in. hardened gelatin against a background of residual silver halide in unhardened waterdispersible gelatin by incorporating the tanning develop ing agent in the form of a precursor, which is compatible with silver halide, with the other normal constituents of silver halide gelatin emulsion layers and inert to atmospheric oxygen, but which liberates the active tanning photographic developing agent on treatment with an alkaline solution having a pH of at least 8.5.

It is therefore an object of our invention to provide silver halide developing agent precursors which can be incorporated with light-sensitive silver halide and because of their stability are photographically compatible until the coating containing them is treated with an activating solution that causes a conversion of the developing agent precursor to an active developer and provides a pH that is high enough to cause the developing agent thus formed to reduce photographically exposed silver halide to silver.

Another object is to provide silver halide photographic materials which have the precursor substances incorporated in the emulsion layers, or layers adjacent thereto. A further object is to provide developing agent precursors for the tanning development of the emulsion layers.

Another object is to provide developing agent precursors which on incorporation into silver halide emulsion layers exert a desirable antifoggant action on the silver halide.

Still another object is to provide a method of processing the emulsion layers of the invention. 4

The above objects are accomplished by incorporating certain Diels-Alder adducts as developing agent precursors in silver halide emulsion layers, or in layers contiguous thereto and, after photographic exposure, treating with an alkaline solution, such as aqueous sodium carbonate, which treatment causes to be formed an active developing agent in the layers.

The developing agent precursors (Diels-Alder adducts) of our invention are illustrated by the following general formula:

wherein R and R represent a hydrogen atom, an alkyl group (for example, alkyl groups containing about 1 to 20 carbon atoms, such as methyl, propyl, amyl, decyl, tridecyl, eicosyl, etc.), an aryl group (for example, an aryl group such as phenyl, tolyl, xylyl, etc.), hydroxy, a sulfonic acid group, halogen, amino group (for example, amino groups such as NH NHR or NR in which R is a lower alkyl group), or a substituted thio group (for example, such as SY wherein Y represents an isocyclic group (for example, an isocyclic group such as phenyl, naphthyl, etc.), or a heterocyclic group (for example a heterocyclic group such as tetrazolyl, a thiazolyl, a quinolinyl, etc.); R R R and R represent a hydrogen atom, a halogen atom, an aryl group (for example an aryl group such as phenyl, tolyl, xylyl, etc.) or a lower alkyl group (for example, methyl, ethyl, propyl, butyl, amyl, etc.); X represents a hydrogen atom on each of the 5 and 8 carbon atoms, a methylene or ethylene group attached to the 5 and 8 carbon atom, which groups may be optionally substituted wtih a halogen atom, an aryl group (for example, those enumerated above), or a lower alkyl group (for example, an alkyl group such as methyl, ethyl, propyl, butyl, amyl, etc.).

The following examples illustrate the preferred types of developer precursors represented by the above general formulas:

( 1) 6,7-dimethyl-4a,5,8,8a-tetrahydro-1,4-naphthoquinone (2) 5,8-methano-4a,5,8,8a-tetrahydro-1,4-naphthoquinone (3) 5,8-ethano-4a,5,8,8a-tetrahydro-1,4-naphtl1oquinone (4) 5,8-ethano-6-methyl-9-is0propyl-4a,5,8,8a-tetrahydro- 1,4-naphthoquinone (5) 2,6,7-trimethyl-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone a: m: g to (6) 2,3-dimethyl-1,4,4a,9a-tetrahydro-9, IO-anthraquinone m m gm w re (7) 2-t-butyl-6,7-dimethyl-4a,5,8,8a-tetrahydro-1,4-

uaphthoquinone l CH i H2 (8) 2-t-buty1-5 ,8-methano-4a,5 ,8,8a-tetrahydro- 1 ,4-

naphthoquinone 4 (9) 2-t-butyl-5,8-e-thano-4a,5,8,8a-tetrahydro-1,4-

naphthoquinone w g-I 47 (10) 2,4a,6,7-tetramethyl-4a,5,8,8a-tetrahydro-1,4-

10 naphthoquinone l 1) 6,7-dimethyl-2-octadecy1-4a,5,8,8a-tetrahydro-1,4-

naphthoquinone CH H2 12 5,6,7,8,9,9-hexachl0ro-5,8-methano-4a,5,8,8a-

tetrahydro-1,4-naphthoquinone (13) 5,8-methano-2-iso-propyl-4a,5,8,8a-tetrahydro l,4-

naphthoquinone (14) 5,8-methano-2-methyl-4a,5,8,8a-tetrahydro-1,4-

naphthaquiuone gai E a 15) 5,8-ethano-7-methy1-6-iso-propyl-4a,5,8,8a-tetrahydro-l ,4-naphtho quinone CH CH '37 l6) 6,7-dimethyl-2-sulfo-4a,5,8,8a-tetrahydro-1,4-

(19) 5,8-ethano-2-(p-tolyl)-4a,5,8,8a-tetrahydro-1,4-

naphthoquinone (20) 5,8 ethano Z-hydroxy 4a,5,8,8a-tetrahydro-1,4-

naphthoquinone (21) 6,7 dimethyl-2-(l-phenyl-S-tetrazolylthio)-4a,5,8,

Sa-tetra-hydro-1,4-naphthoquinone 6 (23) 5,8 methano-2-(l-phenyl-S-tetrazolylthio)-4a,5,8,

8a-tetra-hydro-1,4-naphthoquinone (24) 5,8 ethano-2-(l-phenyl-S-tetrazolylthio)-4a,5,8,8a-

tetraehydro-1,4-naphthoquinone The preparation of these adducts is well known. They are generally formed by the interaction between a quinone such as p-benzoquinone, toluquinone, 1,4-naphthoqu-inone, 2- (t butyl)-p-benzoquinone, t-butyl-p-benzoquinone, pxyloquinone, etc. and a diene, such as cyclopentadiene, cyclohexadiene, c: phellandrene, dimethylbutadiene, hexachlorocyclopentadiene, etc.

For example, Compound 1 was prepared as follows:

A solution of 11.4 g. of p-benzoquinone and 9.5 g. of 2,3-dimethylbutadiene in ml. of benzene was refluxed overnight. The solvent was evaporated under vacuum. The residual yellow solid was recrystallized from methanol, yielding 16 g. of product, M.P. -1 17 (ref. US. .Patent 2,262,002).

The other compounds listed above (i.e., No. 2 to No. 24) were similarly prepared using the reactants given in Table I below.

TABLE I Cpd Diene Dienophile M.P. or B.P. Reference No. of Product, 0

2 1,3-cyclopentadiene p-Benzoquinone M.P. 7678 J. Chem. Soc.

1511 (1935) 3 l,3-cyclohexadiene do M.P. 9294 Bfi32 9,) 337 4 a-Phellandrened0 M.P. 118-120-. Ber 229,)2365 5 zfildimethylbuta- Toluquinone M.P. 91-93 ene. 6 --do 1,4naphthoquinone M.P 148-151.. 7 do t-Butyl-p-benzoquinone Oil 8 1,3-cyclopentadieue.-.. do M? 63-64.... 9 1,3eyel0hexadiene do M.P 85-86--.. 10 2,3-dimethy1butap-Xylo qulnone B.P at 10 Ber 68, 1747 diene. mm. (1935). 11 do Octadecyl-p-benzo- M.P. 64-65-- quinone. 12 Hexachlorocyclop-Benzoquinone M.P.

pentadiene. 13 1,&eyc1opentadiene Iso-propyl-p-benzo- M.P. 49-51-"- quinone. 14.-. (in Toluquinnnp 15---" 3-methyl-2-isopr0pylp-Benz0quin0ne 1,3-cyelohexadiene. 16- 2,3dimethylbuta- SulIo-p-benzoquinone diene. sodium salt. 17 1,3-cyc1opentadiene do 18--- 1,3-cyclohexadiene'. Toluqninnna 19 do p-Tolyl-p-benzoquinone- M.P. 105106 20- do Hydroxy-p-benzoqui- M.P. 187-188-.

none. 21 2,8-dimethylbuta- (1-phenyI-5tetrazolyl- M.P. 127-129.

diene. thio)-p-benzoquinone. 22 do 2-(1-phenyl-5-tetrazolylthi0)-5-methyl-pbenzoquinone. 23"--. 1,3-cyc1opentadiene (l-phenyl-Metrazolyl- M.P. 133-134-.

thio)-p-benzoquinone. 24"- l,3'cyclohexadiene do M.P. 132-133-- (22) 2 l-phenyl-S-tetrazolylthao)-4a,6,7-tnmethyl-4a,5, Example 1 8,8a-tetrahydro-1,4-naphthoquinone Ten grams of 2 isopropyl 5,8-methano-4a,5,8,8atetrahydro 1,4 naphthoquinone were added per silver mole of a medium-speed gelatin-silver bromoiodide photographic emulsion which was then coated on a cellulose acetate film support to yield a silver coverage of 725 mg./sq. ft. and a gelatin coverage of 1210 mg./sq. ft. The untreated emulsion was similarly coated to act as a control. Samples of the control and the test emulsion 5 DK-50 5 S.D. Bath Feature 7 Rel. Spd. 1 Fog Rel. Spd. -y Fog No image.

These data indicate that the subject addenda were substantially inert in the emulsion until activated by the alkaline S.D. bath; when so activated, they produced a useful image, whereas under the same processing conditions the control coating did not exhibit any image.

Single layer coatings of a medium speed gelatin-silver bromoiodide photographic emulsion were prepared which contained 725 mg./ft. of silver, 1200 n1g./ft. of gelatin, and the developer precursors respectively as shown in Table II below. The concentrations of the precursors used in the respective coatings are given in this table. A control (i.e. one containing no developer precursor) containing the same level of silver and gelatin as those described above was also prepared;

Samples of these coatings were exposed in an Eastman 1B Sensitometer and processed for 5 minutes at 72 F. in Kodak DK-SO Developer, fixed in Kodax F5 fix, washed and dried to yield the results described in Table 11 below.

TABLE II Developer 5 DK-50 Fresh Tests 5 D1550 Precursor Coating No. (No.), Oonc.,

gm./mo1e AG Rel. Spd. 7 Fog Incubation 91 1. 08 15 29 100 1. 22 0.10 Q 32 100 1. a2 09 24 100 o. 92 0.12 28 105 1. 42 10 1 100 1. 17 11 20 Coatings incubated for Lyme]; at 120 F. at 50% relative humidity then exposed and processed as described previously.

1 As can be seen from the results in Table II above, the compounds of our invention can be incorporated into emulsion layers and generally causeno deleterious efiect on the elfective speed of the silver halide emulsion. In

8 addition, the coatings containing the respective compounds exhibit improved stability on keeping relative to that of the control.

Since the testing of many possible variations of new compound is laborious and extremely time-consuming, a spot-test was devised to readily ascertain the efiect of a variety of Diels-Alder adducts as potentially useful emulsion-incorporated developer agents. In these tests alkaline solutions of the diels-alded adduct agent as described,

below were streaked across exposed and unexposed areas of a gelatin-silver-chloride emulsion on a paper support. and allowed to stand for four minutes at 72 F.

Spot-test activator I (carbonate):

The acetonitrile is used in the above activator solutions to aid in dissolving the experimental developer agents.

The degree of image development was then qualitatively rated as follows in Table III:

+'+Full development +--Intermediate development 0No development activity TAB LE III Development Activity Developer Coating No. Precursor (No.)

Activator I Activator II (Carbonate) (Hydroxide) Qualitatively rated as described above.

Example 2 In 3 cc. of acetone, 0.3 of a gram of the Compound 1 in Table H was dissolved. The acetone solution was slowly added to 10 cc., 0.03 of a mole of. a slow speed silver chloride emulsion, to which had been added 5 cc. of 10 percent bone gelatin. (Total gelatin content 250 g./1nole.) The mixture was coated on film base at the rate of 450 sq. ft./ mole and dried. Au exposed sample was bathed in 1 percent sodium hydroxide solution for halide emulsion, or colloidal dispersion of a water-pen meable hydrophilie colloid suitable for preparing an undercoat or an overcoat for such silver halide emulsion,

by mixing a solution or dispersion of the precursor compound with the silver halide emulsion, or dispersion of hydrophilic colloid, prior to coating. For example, a developer precursor can be made up as an oil dispersion by stirring a solution of 10 grams of the developing agent precursor into 40 grams of warm tricresylphosphate, and then mixing this solution with 100 grams of a 10 percent aqueous gelatin solution containing 10 cc. of a percent aqueous solution of an alkylnaphthylene sodium sulfonate wetting agent. The resulting dispersion can then be homogenized by passing for 5 times through a colloid mill to produce a homogeneous colloid dispersion. Solvents other than tricresylphosphate can be employed, including any of the crystalloidal compounds described in Jelley and Vitt-ume U.S. Patent 2,322,027, issued June 15, 1943. The resulting colloidal dispersion can then be added to an ordinary silver halide emulsion, or a dispersion of a water-permeable hydrophilic colloid, adapted for preparation of an undercoat or overcoat for such silver halide emulsion.

Instead of adding the oil dispersion directly to the liquid silver halide emulsion or colloidal dispersion, it can be dried for storage purposes and then be reconstituted for use by merely mixing with water.

The developing agent precursors of our invention can be adapted for addition to a liquid silver halide emulsion or colloidal dispersion by other means as well. Suitable methods will depend largely upon the solubility characteristics, particularly in water or polar solvents, of the particular precursors in question.

After addition of the dispersion or solution of the developing agent precursor substance to the liquid emulsion or colloidal dispersion, the mixture is stirred to assure uniform results, or passed through a blending device, such as a colloid mill or Waring Blendor. A uniform coating can then be made on a suitable support and the coating dried. Suitable supports comprise any of the well known supporting materials, such as cellulose ester film base (e.g., cellulose acetate, cellulose nitrate, cellulose acetate butyrate, cellulose acetate propionate, etc.), polyethylene, polypropylene, polystyrene, polyethylene terephthalate and other polyesters, paper, polycarbonates, etc.

The photographic elements of our invention comprising a photographic development precursor either in the photographic silver halide emulsion layer, or layer contiguous thereto, or both, can then be exposed to an original or negative and developed by merely treating the exposed emulsion layer with an alkaline activator bath. Typical activator baths comprise, for example, an aqueous solution of an alkaline material, such as sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, mixtures of sodium hydroxide and sodium sulfite, etc. Suitable baths can comprise, for example an aqueous solution containing about 1 percent sodium hydroxide and 5 percent sodium sulfite. A bath of the latter type is quite suitable for developing an exposed emulsion 'layer in about 30 seconds when the activator bath is at about 68 F. Modifications can easily be made in the activator baths without departing from the spirit and scope of the invention. For example, an aqueous solution comprising about 4 percent of sodium carbonate and 5 percent of sodium sulfite produces development in about 30 seconds at 68 F. Another aqueous activator solution comprising 2 percent sodium hydroxide and 5 percent sodium sulfite produces useful photographic images in a few seconds when heated at 130 F. Particularly useful activator solutions have a pH of at least about 9.0 and preferably of at least about 10.5.

The activator solutions of the present invention can be applied to an exposed photographic element in any number of known ways, such as by dipping, spraying, or other suitable surface applications. If desired, a thickener can be added to the activator solution to increase the viscosity of the composition and make it more adaptable for continuous processing. Viscous compositions can then be 10 removed by squeegeeing or water spraying. The photographic element can then be stabilized by conventional fixation or stabilization, such as by sodium thiosulfate.

The concentration of the precursors used in our invention will vary, depending upon the particular chemical compound involved and the location of the compound within the photographic element. That is, if the precursor is incorporated within the silver halide emulsion undergoing development, it may be desirable to use a somewhat dilferent concentration than would be used if the precursor were incorporated in a layer contiguous to the photographic silver halide emulsion. A useful concentration of precursor for incorporation in the emulsion is from about 0.01 to 4.0 moles per mole of silver halide. A particularly useful range is from about 0.1 to 2.0 moles per mole of silver halide, with especially useful results being obtained within the range of about 0.4 to 1.0 mole per mole of silver halide. For incorporation in a layer contiguous to the silver halide emulsion layer, somewhat larger concentrations of precursor can be tolerated without adverse effects. A particularly useful eifect of our invention is that even when incorporated within the silver halide emulsion, the precursors have little or no desensitizing effects. In many cases, thi is not true Where developing agents, per se, are incorporated within the silver halide emulsion layers.

Photographic silver halide emulsions useful in our invention comprise any of the ordinarily employed silver halide developing out emulsions, such as, silver-chloride, -chlorobromide, -chloroiodide, -chlorobromoiodide, -bromide and -brornoiodide developing-out emulsions. Any of the conventionally employed water-permeable hydrophilic colloids can be employed in the silver halide emulsions, or in layer contiguous thereto. Typical Waterpermeable hydrophilic colloids include gelatin, albumin, polyvinyl alcohol, agar agar, sodium alginate, hydrolyzed cellulose esters, hydrophilic polyvinyl copo'lymers, etc.

Photographic silver halide emulsions useful in our invention can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamate, thiourea, allyl isothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.). (See U.S. Patents 2,540,085, 2,597,856 and 2,597,915, etc.)

Photographic silver halide emulsions useful in our invention can also be sensitized by other means, such as by alkylene oxide polymers, many of which are well known to those skilled in the photographic art. Typical polyalkylene oxide polymers include those of U.S. Patents 2,423,549 and 2,441,389.

The emulsions of the invention can also contain speedincreasing compounds of the quaternary ammonium type as described in U.S. Patents 2,271,623, issued February 3, 1942; 2,288,226, issued June 30, 1942; 2,334,864, issued November 23, 1943; or the thiopolymers as described in Graham et al., U.S. application Serial No. 779,839, filed December 12, 1958, now U.S. Patent No. 3,046,129; and Dann et al., U.S. application Serial No. 779,874, filed December 12, 1958, now U.S. Patent No. 3,046,134.

The emulsions may also be chemically sensitized with reducing agent such as stannous salts (Carroll U.S. Patent 2,487,850), polyamines such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698), polyamines such as spermine, (Lowe and Allen U.S. Patent 2,521,925), or bis-(B-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926)

The emulsions may also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. application Serial No. 319,611; Carroll and Murray U.S. application Serial No. 319,612; and Leubner and Murray U.S. ap plication Serial No. 319,613, all filed November 8, 1952, now U.S. Patents 2,728,663, 2,728,664, and 2,728,665, respectively, granted December 27, 1955.

The addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions, they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used. The agents may be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type, such as described in Godowsky, U.S. Patent 2,698,- 794, issued January 9, 1955; or emulsions of the mixed grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243.

It has been found that the development rate of the precursors above can be improved by adding an auxiliary developing agent either to the silver halide emulsion layer, or a hydrophilic layer contiguous thereto. Typical auxiliary developing agents include those described in the copending application Serial No. 134,014, filed August 5, 1961, and now abandoned, of P. H. Stewart, G. E. Fallesen and I. W. Reeves, Jr. Typical auxiliary developing agents described in this application include 3-pyrazolidone compounds containing an alkyl (e.g., methyl, ethyl, etc.) or aryl substituent (e.g., phenyl, p-tolyl, etc.).' In addition, such pyrazolidone developing agents can contain an I acyl or acyloxy substituent which can be hydrolyzed from the 3-pyrazolidone compound by treatment with the above activator solutions to produce the desired auxiliary developing compound. Typical auxiliary developing agents include, for example,

1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 3-acetoxy-l-phenyl-3-pyrazolidone (enol ester), Z-(pyridinium acetyl)-1-phenyl-3-pyrazolidone chloride, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-2-benzoyl-3-pyrazolidone, 1-phenyl-2-lauroyl-3-pyrazolidone, 1-phenyl-2-chloroacetyl-3-pyrazolidone, etc.

The concentration of auxiliary developing agents can be varied and, of course, no auxiliary developing agent need be employed unless so desired. Useful concentrations of auxiliary developing agents vary from about 0.01 mole to 2.0 moles per mole of developing agent precursor compound. Depending upon the particular auxiliary developing agent employed, larger or smaller quantities can be used.

The developer precursors of our invention can be used in emulsions intended for use in dilfusion transfer processes which utilized the undeveloped silver halide in the nonimage areas of thenegative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land U.S. Patents 2,584,029, issued January 29, 1952; 2,698,236, issued December 28, 1954, and 2,543,181, issued February 27, 1951; and Yackel et a1. U.S. Patent 3,020,155, issued February 6, 1962. They may also be used. in color transfer processes which utilize the diffusion transfer of an image-wise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another. Color processes of this type are described in Land U.S. Patents 2,559,643, issued July 10, 1951, and 2,698,798, issued January 4, 1955; Land and Rogers Belgian Patents 554,933 and 554,934, granted August 12, 1957; International Polaroid Belgian Patents 554,212, granted July 16, 1957, and 554,935, granted August 12, 1957; Yutzy U.S. Patent 2,756,142, granted July 24, 1956, and Whitmore and Mader U.S. patent application Serial No. 734,141, filed May 9, 1958, and now abandoned. They may also 12 be used in emulsions intended for use in a monobath process such as described in Haist et al. U.S. Patent 2,875,048, issued February 24, 1959, and in web-type processes, such as the one described in Tregullus et al. U.S. patent application Serial No. 835,473, filed August 24, 1959, now U.S. Patent No. 3,179,517.

Of course, the activator solutions which are used in our invention are stable for extended periods of time and are not subject to-the harmful decomposition reactions so common to conventional photographic developing ;solutions when these developing solutions are stored for extended periods of time. No special precautions are required to prevent oxidation of the activator solutions since they are inherently quite stable. If desired, the activator solutions can be incorporated in a carrier, such as gelatin and coated in contact with the photographic silver halide emulsion layer which contains the development precursors of our invention. After exposure, the development can be effected merely by heating the photographic emulsion layer to a temperature sufiicient to release Water, which may be present in the support or in a separate layer in the photographic element.

takes it into the photographic halide emulsion layer where development is effected.

The elevated temperatures from about 150 C. are

usually sufiicient to efiect development in this manner. If desired, additional moisture can be added by spraying steam upon the sensitive surface of the photographic ele ment.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended 5 claims.

We claim:

1. A photographic element comprising a support and a photographic silver halide emulsion layer, and integral with said photographic element a water-permeable hydrophilic colloid layer containing a compound selected from the class of compounds represented by the following general formulas:

halogen, an aryl group, and a lower alkyl group; X

represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methyL ene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member selected from the class consisting of a halogen, an aryl group and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

2. A photographic element comprising a support and a photographic water-permeable hydrophilic colloid silver halide emulsion layer containing a compound selected This Water then dissolves the activator solution from the hydrophilic colloid layers and from the class of compounds represented by the following general formulas:

s (III) s I'M R R1 R A B I X and X R Y-R, R,- Y R R. (I R. 6 1'1.

I II wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a. methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and v8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

3. A photographic element comprising a paper support and a photographic silver halide emulsion layer, and integral with said photographic element a water-permeable hydrophilic colloid layer containing a compund selected from the class of compounds represented by the following general formulas:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and av substituted thio group S-Y, wherein Y represents a member selected from the class consisting of an isocyclicv group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen,- an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the S and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

4. -A photographic element comprising a support and a photographic silver halide emulsion layer, and integral with said photographic element, a colloidal dispersion of a compound in a water-insoluble, water-permeable crystalloidal solvent, said compound being selected from the class of compounds represented by the following general formulas:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

5. A photographic element according to claim 4 wherein said crystalloidal solvent is a high-boiling ester of a phenol.

6. A photographic element according to claim 5 wherein said high-boiling ester is tricresylphosphate.

7. A photographic element comprising a paper support and a photographic silver halide emulsion layer, and integral with said photographic element a water-permeable, hydrophilic colloid layer containing (a) a compound selected from the class of compounds represented by the following general formulas:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methyl ene and ethylene grups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms, and (b) a 3-pyrazolidone photographicdevelopmg agent.

8. A photographic element comprising a flexible support and a photographic silver halide emulsion layer, and integral with said photographic element a waterpermeable hydrophilic colloid layer containing a compound selected from the class of compounds represented by the following general formulas:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid II R5 I II R4 VB:

group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

9. A photographic element comprising a support and a photographic silver halide gelatino emulsion layer containing a compound selected from the class of compounds represented by the following general formulas:

I II I R R1 R5 R5 I X I and X R4 R: R R4 I II I R] 0 R3 0 R5 I II wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio radical S-Y, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

10. A photographic element comprising a support and a photographic silver halide untanned gelatino emulsion layer containing a compound selected from the class of conlrpounds represented by the following general formu as:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms,

a methylene attached to the 5 and 8 carbon atoms, an'

ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a :member of the group selected from the class consisting of a halogen, auaryl group, and the lower alkyl groups,

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X

represents a member selected from the class consisting I of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 canbon atoms, an ethylene group attached to the ,5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, and methylene and ethylene groups attached to the five and eight carbon atoms.

12. A photographic element comprising a support and a photographic, water-permeable, hydrophilic, silver halide emulsion layer containing a compound selected from the class of compounds represented by the following general formula:

Ra I0 R4 RUQU Q? Y I R; 0 R5 wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group, and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an arylgroup, and lower alkyl groups, said methylene and ethylene groups attached to the five and eight carbon atoms.

13. A process for forming a visible photographic image comprising developing a photoexposed photographic element comprising a support and a photographic silver halide emulsion layer, and integral with said photographic element a water-permeable, hydrophilic colloid layer containing a compound selected from the class of compounds represented by the following general forwherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups,

said methylene and ethylene groups attached to the five.

and eight carbon atoms by imbibing throughout said photographic silver halide emulsion layer an aqueous alkaline solution containing sufficient alkali to give a pH of at least about 9.0.

14. A process for forming a photoresist comprising exposing a photographic silver halide emulsion layer containing a compound selected from the class of compounds represented by the following general formulas:

wherein R and R represent a member selected from the class consisting of hydrogen, an alkyl group from 1 to 20 carbon atoms, an aryl group, hydroxy, a sulfonic acid group, halogen, amino and a substituted thio group --SY, wherein Y represents a member selected from the class consisting of an isocyclic group and a heterocyclic group, wherein R R R and R represent a member selected from the class consisting of hydrogen, halogen, an aryl group and a lower alkyl group; X represents a member selected from the class consisting of a hydrogen on each of the 5 and 8 carbon atoms, a methylene attached to the 5 and 8 carbon atoms, an ethylene group attached to the 5 and 8 carbon atoms and methylene and ethylene groups, said methylene and ethylene groups attached to the five and eight carbon atoms substituted with a member of the group selected from the class consisting of a halogen, an aryl group, and lower alkyl groups, developing in an alkaline bath, and removing the untanned areas in warm water.

15. A photographic element as defined in claim 1 wherein said precursor is 6,7-dimethyl-4a,5,8,8a-tetrahydro-1,4-naphthoquinone.

16. A photographic element as defined in claim 1 wherein said precursor is 5,8-methano-4a,5,8,8a-tetrahydro-1,4-naphthoquinone.

17. A photographic element as defined in claim 1 wherein said precursor is 5,8-ethano-4a,5,8,Sa-tetrahydro-l,4-napl1thoquinone.

18. A photographic element as defined in claim 1 wherein said precursor is 2,6,7-trimethyl-4a,5,8,8a-tetrahydro-1 ,4-naphthoquinone.

19. A photographic element as defined in claim 1 wherein said precursor is 5,8-methano-2-methyl-4a,5,8, 8a-tetrahydro-1,4-naphthoquinone.

20. A photographic element as defined in claim 1 wherein said precursor is 6,7-dimethyl-2-(1-phenyl5- tetrazolylthio -4a,5,8,8a-tetrahydro-1,4-naphthoquinone.

References Cited by the Examiner UNITED STATES PATENTS 2,206,126 7/1940 Schinzel 96-55 2,592,368 4/1952 Yackel 96-95 2,716,059 8/1955 Yutzy et al. 96-95 2,892,710 6/1959 Cohler et al 96-95 FOREIGN PATENTS 624,219 7/ 1961 Canada.

OTHER REFERENCES British Journal of Photography, Apr. 14, 1939, pp. 230 and 231.

Conant, et al.: The Chemistry of Organic Chemistry, 4th ed., 1954, The Macmillan Co., pp. 459, 538 and 539.

Forster et al.: The Photographic Journal, November 1933 pp. 466-470.

Glafkides: Photographic Chemistry, vol. 2, 1960, Fountain Press, London, p. 714.

Mees: The Theory of the Photographic Process, 1954, The Macmillan Co., N.Y., pp. 546-554 and 577-584.

NORMAN G. TORCHIN, Primary Examiner.

A. D. RICCI, Assistant Exdminer. 

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND A PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER, AND INTEGRAL WITH SAID PHOTOGRAPHIC ELEMENT A WATER-PERMEABLE HYDROPHILIC COLLOID LAYER CONTAINING A COMPOUND SELECTED FROM THE CLASS OF COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULAS:
 14. A PROCESS FOR FORMING A PHOTORESIST COMPRISING EXPOSNG A PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER CONTAINING A COMPOUND SELECTED FROM THE CLASS OF COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULAS: 2-R1,3-R2,5-R3,5,8-(-X-),6-R4,7-R5,8-R6-1,4,4A,5,8,8AHEXAHYDRONAPHTHALENE -1,4-DIONE AND 1,3,6-TRI(R4-),2,4,7-TRI(R5-),5-R3,5,8-(-X-),8-R6-5,8,8A, 9,10,10A-HEXAHYDROANTHRACENE-9,10-DIONE WHEREIN R1 AND R2 REPRESENT A MEMBER SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, AN ALKYL GROUP FROM 1 TO 20 CARBON ATOMS, AN ARYL GROUP, HYDROXY, A SULFONIC ACID GROUP, HALOGEN, AMINO AND A SUBSTITUTED THIO GROUP -S-Y, WHEREIN Y REPRESENTS A MEMBER SELECTED FROM THE CLASS CONSISTING OF AN ISOCYCLIC GROUP AND A HETEROCYCLIC GROUP, WHEREIN R3, R4, R5 AND R6 REPRESENT A MEMBER SELECTED FROM THE CLASS CONSISTING OF HYDROGEN HALOGEN, AN ARYL GROUP AND A LOWER ALKYL GROUP; X REPRESENTS A MEMBER SELECTED FROM THE CLASS CONSISTING OF A HYDROEN ON EACH OF THE 5 AND 8 CARBON ATOMS, A METHYLENE ATTACHED TO THE 5 AND 8 CARBON ATOMS, AN ETHYLENE GROUP ATTACHED TO THE 5 AND 8 CARBON ATOMS AND METHYLENE AND ETHYLENE GROUPS, SAID METHYLENE AND ETHYLENE GROUPS ATTACHED TO THE FIVE AND EIGHT CARBON ATOMS SUBSTITUTED WITH A MEMBER OF THE GROUP SELECTED FROM THE CLASS CONSISTING OF A HALOGEN, AN ARYL GROUP, AND LOWER ALKYL GROUPS, DEVELOPING IN AN ALKALINE BATH, AND REMOVING THE UNTANNED AREAS IN WARM WATER. 